WO2004067657A1

WO2004067657A1 - Multicolor coating compositions and method of forming patterned surface

Info

Publication number: WO2004067657A1
Application number: PCT/JP2003/009974
Authority: WO
Inventors: Yoshikazu Ishida; Seigou Yano
Original assignee: Sk Kaken Co., Ltd.
Priority date: 2003-01-31
Filing date: 2003-08-06
Publication date: 2004-08-12
Also published as: TW200413488A; HK1083224A1; MY136045A; KR100678760B1; KR20050094866A; AU2003252412A1; TWI328601B

Abstract

Practical water-in-water type multicolor coating compositions capable of forming a coating film having excellent surface smoothness; and a method of coating with the coating compositions. One of the water-in-water type multicolor coating compositions is characterized by comprising a matte clear coating material containing a water-compatible resin and a loading pigment having a refractive index of 1.4 to 1.7 and, dispersed in the coating material, at least one kind of flat colored gel particles. The other water-in-water type multicolor coating composition is characterized by comprising a clear coating material containing a water-compatible resin and, dispersed in the coating material, at least one kind of flat colored gel particles, the flat gel particles being a gel derived from a water-compatible resin (a), a coloring pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water. Also provided is a method of forming a patterned surface, characterized by applying a colored matte primer coating material on a building as a base to form a primer layer and then applying the water-in-water type multicolor coating composition by roll coating or brush coating to form a topcoat layer.

Description

Multi-pattern paint composition, method of forming patterned surface

TECHNICAL FIELD The present invention relates to a novel water-in-water type colorful pattern paint composition. Background art

Conventionally, when painting interior and exterior surfaces of buildings such as walls, ceilings and doors, paints generally called flat paints are often used. As the flat paint, a paint specified in JIS K5663 “Synthetic resin emulsion paint” is typical. Such a flat paint can express various colors by toning with a pigment. However, the color obtained by flat paint is a single color, and it is not possible to display a pattern in which multiple colors are mixed in one painting.

On the other hand, there have been proposed various paint compositions capable of displaying various patterns by one coating. The idea of the composition of such paints began with the patent of P. BUSCH, and by J.C. ZOLA, U.S. Pat. No. 2,591,904 and three patents, No. 2,31,698. _C ) Various paints have been developed by paint engineers in Japan and abroad. These are i) oil-in-water (O / W), ii) water-in-oil type (W / O type), iii) oil-in-oil type (O / O type), and iv) water-in-water type (W / W type).

For example, Japanese Patent Application Laid-Open No. 9-320281 discloses an enamel obtained by dispersing an enamel obtained by using a copolymer containing a crosslinkable functional group in an aqueous dispersion medium and then mixing a crosslinkable component. Multi-pattern paints containing dispersed particles are described. However, the paint described in this publication is an oil-in-water type colorful paint containing an organic solvent in the enamel-dispersed particles, and generates a solvent smell when dried. Further, since the enamel-dispersed particles disclosed in this publication have high hardness and a substantially spherical three-dimensional shape, it is difficult to form a smooth coating film.

In an underwater water-based colorful pattern paint in which aqueous particles are dispersed in an aqueous medium, as described above, The problem of generation of a bad odor can be greatly improved. An example of such a water-in-water type colorful pattern paint is the paint described in Japanese Patent No. 2615533. The coating material of this publication contains flaky gel colored particles derived from sodium alginate, polybutyl alcohol, and the like, and hollow particles such as a hollow resin foam and an inorganic balun. The use of the paint of the publication makes it possible to form a relatively smooth coating film. However, in the paint disclosed in this publication, since the hollow particles have light scattering properties, the formed coating film becomes whitish, resulting in a finish lacking sharpness. As other water-in-water type colorful pattern paints, for example, paints described in Japanese Patent No. 2525197 are mentioned.

However, the colored particles described in this publication are encapsulated particles, and the particles contain a liquid aqueous paint. For this reason, depending on the coating conditions, the capsule may be destroyed and a desired pattern may not be formed. In particular, when a roller is painted or a brush is painted, problems such as color oozing out of the particles are likely to occur. Further, since the paint in the publication is liquid in the capsule, there is also a problem that the formed pattern fluctuates due to the temperature and the coating pressure during coating. DISCLOSURE OF THE INVENTION ''

The present invention has been made in view of the above points, and an object of the present invention is to provide a practical water-in-water type colorful pattern paint capable of forming a coating film having excellent smoothness and a method for applying the same. is there.

A first object of the present invention is to obtain a water-in-water type colorful pattern paint capable of forming a matte coating film having excellent smoothness and sharpness.

A second object of the present invention is to provide an underwater water-colored multi-color paint capable of forming a constant smooth multi-color pattern even when coating conditions such as a coating tool and a coating temperature fluctuate. The problem is to obtain a coating method that can form a colorful and smooth coating surface by roller coating or brush coating.

In order to solve these problems, the inventor has conducted intensive studies.

As a result, by dispersing the flat colored gel particles in a matte transparent paint containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7, the first section can be obtained. We found that the problem could be solved.

Further, as the flat colored gel particles, a gelled product derived from an aqueous resin (a), a colored pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water is employed. Thus, they have found that the second problem can be solved.

That is, the present invention has the following features.

1. Characterized by at least one kind of flat colored gel particles dispersed in a matte transparent coating containing an extender pigment having an aqueous resin and a refractive index of 1.4 to 1.7. A water-in-water type multi-color paint composition.

2. At least one kind of flat colored gel particles is dispersed in a matte transparent coating containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7,

The flat colored gel particles are gelled products derived from an aqueous resin (a), a coloring pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water. Water-based multi-color paint composition.

3. At least one kind of flat colored gel particles is dispersed in a matte clear coating containing an aqueous resin, a 'and an extender having a refractive index of 1.4 to 1.7,

The flat colored gel particles,

It is gelled by mixing an aqueous paint containing an aqueous resin (a), a color pigment (b), and water (c) with a reactive compound (d) capable of reacting in the presence of water. Water-based multi-color paint composition.

4. At least one kind of flat colored gel particles is dispersed in a transparent paint containing an aqueous resin,

5. In a transparent paint containing an aqueous resin, at least one kind of flat colored gel particles is dispersed,

The flat colored gel particles,

It must be gelled by mixing an aqueous paint containing an aqueous resin (a), a color pigment (b), and water (c) with a reactive compound (d) that can react in the presence of water. Characteristic underwater water-colored multi-color paint composition.

6. The component (a) is an aqueous resin (a-1) having a reactive functional group, and the component (d) is a reactive compound capable of reacting with the component (a-1) in the presence of water. d-1) The water-in-water multicolor paint composition according to any one of 2. to 5. above.

7. The water-in-water multicolor paint composition according to any one of 2. to 5., wherein the component (d) is a reactive compound (d-2) capable of self-condensing in the presence of water.

8. At least one flat colored gel particle is dispersed in a matte transparent coating containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7,

The flat colored particles,

An aqueous resin containing an aqueous resin (a-1) having a reactive functional group, a color pigment (b), and water (c) is mixed with a reactive compound (d) capable of reacting in the presence of water. The obtained gelled product is dispersed in an aqueous dispersion medium in the form of flat granules, and further obtained by mixing the reactive compound (d-1) capable of reacting with the component (a-1) in the presence of water. An underwater water-colored multi-color paint composition comprising:

9. At least one kind of flat colored gel particles is dispersed in a transparent paint containing an aqueous resin,

The flat colored particles,

10. The water-in-water multicolor paint composition according to 8 or 9, wherein the component (d) is a reactive compound (d-1) capable of reacting with the component (a-1) in the presence of water. .

1 1. The water-in-water multicolor paint composition according to 8 or 9, wherein the component (d) is a reactive compound (d-2) capable of self-condensing in the presence of water.

1 2. For building materials

After forming an undercoat layer with colored matte undercoat,

1. Roller coating of the underwater water-based multi-color paint composition described in any of 1 to 1 Alternatively, a method of forming a pattern surface characterized by forming an overcoat layer by brush painting.

ADVANTAGE OF THE INVENTION According to this invention, the practical water-in-water type colorful pattern paint which can form the coating film excellent in smoothness can be obtained.

Specifically, by dispersing the flat colored gel particles in a matte transparent paint containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7, excellent smoothness and sharpness are obtained. A water-in-water multicolored pattern paint capable of forming an opaque coating film can be obtained.

Further, by adopting a gelled substance derived from an aqueous resin (a), a colored pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water, as the flat colored gel particles. Thus, it is possible to obtain a water-in-water type multi-pattern paint capable of forming a constant smooth multi-pattern even when coating conditions such as a coating tool and a coating temperature fluctuate.

Further, according to the present invention, a colorful and smooth coating film surface can be formed by roller coating or brush coating of the underwater water-based multi-color paint. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail along with its embodiments.

(Transparent paint)

In the composition of the present invention, a transparent paint is used as a dispersion medium. This transparent coating contains an aqueous resin as an essential component. The degree of the transparency may be such that the flat colored gel particles can be visually recognized and the sharpness is not lost.

The aqueous resin in the transparent paint is a component that plays a role in fixing the colored gel particles when forming a coating film. As such an aqueous resin, a water-dispersible resin and / or a water-soluble resin can be used. Examples of the type of resin include acrylic resin, urethane resin, vinyl acetate resin, silicone resin, fluororesin, acrylic acrylic resin, acrylic urethane resin, acrylic silicone resin, polyvinyl alcohol, and cellulose derivatives. And one or more of these can be used. Such an aqueous resin may have a property of causing a crosslinking reaction after the formation of a coating film. By having such a cross-linking reactivity, the physical properties of the coating film such as water resistance, weather resistance, stain resistance, and chemical resistance can be improved.

In the case of forming a matte paint film, a matte transparent paint is suitable as a dispersion medium. The transparent clear paint can be obtained by mixing a body pigment having a refractive index of 1.4 to 1.7 with the transparent paint. By using such extender pigments in the glossy transparent paint, it is possible to obtain a glossy effect while maintaining the sharpness of the coating film. Examples of extenders that can be used include heavy calcium carbonate, hydrated rock, light calcium carbonate, white carbon, talc, lime ore, clay, porcelain clay, china clay, diatomaceous earth, pearlite powder, barium sulfate, sediment Falling barium sulfate, silica sand, silica powder, quartz powder, resin powder, etc. (excluding hollow products) can be used, and these can be used alone or in combination of two or more. The refractive index is a value measured using an Abbe refractometer.

The average particle diameter of the extender is usually 20 μm or less, preferably 0.1 to 15 μm, and more preferably 0.5 to 8 / zm. By using the extender having such an average particle diameter, the sharpness of the coating film can be further improved. Here, the average particle diameter means a 50% particle diameter measured by a centrifugal sedimentation type particle size distribution analyzer.

The mixing ratio of the extender pigment in the matte transparent paint is usually 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the solid content of the aqueous resin. In addition, the term “glossy” in the present invention includes, in addition to what is generally called “glossy”, what is called “three-way gloss” and “five-minute gloss”. Specifically, in the present invention, the glossiness can be defined by the degree of specular light. The specular glossiness of the above-mentioned matte transparent paint is usually 40 or less, preferably 20 or less, and more preferably 10 or less. Adjustment of the gloss of the transparent matte paint can be appropriately performed depending on the type, particle diameter, mixing ratio, and the like of the extender pigment used in the transparent matte paint.

Here, the specular gloss is a value measured in accordance with JISK540, 7.6 “Specular gloss”. Specifically, paint is applied to one side of a glass plate using a B-type film applicator with a clearance of 150 / zm. This value is obtained by measuring the specular gloss (measuring angle: 60 degrees) when dried at 0 ° C and a relative humidity of 65% for 48 hours.

(Flat colored gel particles)

In the composition of the present invention, flat colored gel particles (hereinafter, also simply referred to as “colored particles”) are dispersed in the above transparent paint. In the present invention, since the colored particles have a flat shape, a smooth coating film can be formed. The term “flat” as used in the present invention means a state in which the ratio of the minor axis to the thickness is greater than 1. The minor axis and major axis of the colored particles are not particularly limited, but are usually from 0.01 to 10 mm, preferably from 0.1 to 5 mm, and more preferably from 0.7 to 2 mm.

At least one kind of colored particles must be contained, but it is desirable that two or more kinds of colored particles having different hues are contained in order to display various pattern surfaces. The hue of the colored particles can be appropriately set according to a desired pattern. As the colored particles, particles having transparency may be included.

The mixing ratio of the colored particles is usually 50 to 1,000 parts by weight, preferably 100 to 900 parts by weight, and more preferably 200 to 800 parts by weight, based on 100 parts by weight of the solid content of the aqueous resin contained in the transparent paint. It is.

As the colored particles in the composition of the present invention, a gelled product derived from an aqueous resin (a), a colored pigment (b), water (c;), and a reactive compound (d) capable of reacting in the presence of water is preferable. It is. Such colored particles have both appropriate flexibility and strength, and can form a constant multicolored pattern even when coating conditions such as coating equipment and coating temperature fluctuate. Furthermore, not only spray coating but also roller coating or brush coating can prevent bleeding or the like due to pigments from colored particles. Therefore, a water-in-water type colorful pattern paint which is also useful for roller coating or brush coating can be obtained.

Specifically, such colored particles are prepared by mixing a reactive compound (d) that can react in the presence of water with an aqueous paint containing an aqueous resin (a), a color pigment (b), and water (c). It can be obtained by gelling the water-based paint in combination and dispersing this gelled substance in the transparent paint. '

The water-based resin in the water-based paint (hereinafter referred to as “component (a)”) serves as a vehicle as a vehicle. Water-dispersible resin and Z or water-soluble resin can be used. Specifically, for example, an acrylic resin emulsion, a urethane resin emulsion, a vinyl acetate resin emulsion, a silicon resin emulsion, a fluororesin emulsion, an acrylic ester resin emulsion, an acrylic resin emulsion, an acrylic resin emulsion, Lil 'silicone resin emulsion, poly (vinyl alcohol), poly (meth) acrylic acid, polyethylene oxide, water-soluble urethane, bio gum, galactomannan derivative, alginic acid or its derivative, cellulose derivative, gelatin, casein, albumin, etc. Alternatively, these may be chemically modified by oxidation, methylation, carboxymethylation, hydroxyshethylation, hydroxypropylation, sulfation, phosphorylation, cationization, and the like. One or more types can be used.

The mixing amount of the component (a) in the water-based paint is usually 3 to 95% by weight, preferably

5-8 0 weight ^_0/0.

As the component (a), an aqueous resin having a reactive functional group (hereinafter, referred to as “(a-1)”) can also be used. Such (a-l) component is described later in (d-

1) It can be suitably used in combination with components.

Examples of the reactive functional group in the component (a-1) include a hydroxyl group, an epoxy group, a hydroxyl group, a carbonyl group, a hydrazino group, an amino group, and an alkoxysilyl group.

As the coloring pigment (hereinafter, referred to as “component (b)”), those generally blended in paints can be used. For example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red iron, molybdate orange, permanent red, permanent carmine, anthraquinone Red, perylene, red, yellow iron oxide, titanium yellow, first toy yellow, benzimidazolone yellow, chrome green, copanoleto green, phthalocyanine green, ultramarine, navy blue, cobalt blue, phthalocyanine blue Quinacridone violet, dioxazine violet, aluminum pigment, pearl pigment, etc. One or more of these may be used. it can.

Mixing amount of the component (b) in the aqueous coating composition is typically 0.0 to 50 wt%, is preferred properly is from 0.5 to 40 weight ^_0/0.

As the dispersant of the component (b), a polymer dispersant is preferable because it can improve the color stability of the colored particles, particularly when stored at a high temperature. The molecular weight of such a polymeric dispersant is usually from 2,000 to 100,000, preferably from 5,000 to 50,000. Specific examples include anionic polymer dispersants, nonionic polymer dispersants, cationic polymer dispersants, and amphoteric polymer dispersants.One or more of these may be used. Can be. Among them, in the present invention, a thiothionic polymer dispersant is particularly preferable.

The HLB of the polymer dispersant is preferably from 3 to 15, and more preferably from 5 to 10. Use of such a polymer dispersant having HLB can further enhance the color stability of the colored particles. HLB is an abbreviation of hydrophilic monolipophilic balance, and is a numerical representation of the intensity ratio of hydrophilicity to lipophilicity of an amphiphilic substance.

The reactive compound capable of reacting in the presence of water (hereinafter, referred to as “component (d)”) is a component that gels the aqueous paint containing the above-described components (a) to (c).

In the present invention, when the component (a-1) is used as the component (a), the component (d) is a reactive compound capable of reacting with the component (a-1) in the presence of water (hereinafter referred to as "( d-1) component)). The combination of the reactive functional groups in the component (a-1) and the component (d-1) is not particularly limited as long as gelling is possible. For example, a carboxyl group and a carpoimide group, a carboxyl group and an epoxy group, a carboxyl group And aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazino group, epoxy group and hydrazino group, epoxy group and amino group, and alkoxysilyl group. One or more of these combinations can be used.

Specific examples of the component (d-1) include, for example, compounds containing a carbodiimide group as described in JP-A-1-0-60272, JP-A-10-316930, JP-A-11-60667. Publications and the like; compounds containing epoxy groups and Polyethylene glycol resin glycidinoleate ether, polyhydroxy phenol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polydaricidyl ether, etc .; 2,2-bishydridyl as a compound containing an aziridine group Roxymethylptano monolithris [3- (1-1-aziridinyl) probione "to], 1,6-hexamethylenediethylene-peryl, diphenyl ^^ methane-bis-1,4,4,1-N, N, diethyleneuree 2-oxanolin-2-oxazoline, 2-vinyl-4-methyl-2-oxoxolin, 2-butyl-15-methyl-2-oxazoline, 2-isopropanol 2- A resin in which a polymerizable oxazoline compound such as oxazoline is copolymerized with a monomer copolymerizable with the compound; Compounds containing a cyanate group include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and derivatives thereof; and compounds containing a hydrazino group include malonate dihydrazide and succinic acid dihydrochloride. Hydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sepasic acid dihydrazide, maleic acid dihydrazide and the like.

As the component (d), a reactive compound capable of self-condensation in the presence of water (hereinafter, referred to as “component (d — 2)”) can also be used. When the component (d-2) is used, the component (a) is not particularly limited, and may be an aqueous resin other than the component (a-1).

As the component (d-2), a hydrolysis-condensation-type reactive compound containing an alkoxysilyl group is suitable. Examples of such a hydrolyzable reactive compound include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-oxysilane, Tetra tert-oxysilane, tetraphenoxysilane, dimethoxydiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane Toxisilane, γ-glycidoxypropylmethyldimethoxy Orchid, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Ν- (j3-aminoethyl) -γ-aminopropyltrimethoxysilane, Ν- (β-aminoethyl) -γ-amino Examples thereof include propylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltrichlorosilane, and the like, and condensates thereof. Also, an alkoxysilane compound containing a carboxyl group, a hydroxyl group, a sulfone group, an oxyalkylene group, or the like can be used. These can be used alone or in combination of two or more. Among them, a tetraalkoxysilane compound is preferably used in the present invention. The tetraalkoxysilane compound is

It is a compound represented by RO- (S i (OR) ₂ -θ) _n -R (where R is an alkyl group, n 1). Particularly, in the present invention, a tetraalkoxysilane compound in which an alkyl group having 1 to 2 carbon atoms and an alkyl group having 3 or more carbon atoms (preferably 3 to 12) are mixed is most preferable.

The mixing amount of the component (d) is usually 0.1 to 10% by weight, and preferably 0.3 to 6% by weight, based on the aqueous paint. (D) When the amount of the component is small, the gel-forming ability becomes insufficient, and the colored particles may be broken at the time of coating (particularly at the time of roller coating or brush coating). If the amount of the component (d) is large, the colored particles become hard, and it becomes difficult to obtain a smooth coating film.

In order to promote the reaction of the component (d), the catalyst of the component (d) can be mixed as necessary. Examples of such a catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid, benzenesulfonic acid, and toluenesulfonic acid; sodium hydroxide, potassium hydroxide, ammonia, and amine compounds. Organotin compounds such as dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate; aluminum tris (acetyl acetate), aluminum monoacetylacetonate bis (ethyl acetate), etc. Organic aluminum compounds; organic titanium compounds such as titanium tetrakis (acetyl acetate); organic zirconium compounds such as zirconium tetrakis (cetyl acetate); boron compounds such as boric acid; (Manufacturing method of colorful pattern paint)

In the production of the composition of the present invention, first, a gelled product is prepared by mixing the component (d) with an aqueous paint containing the components (a) to (c). Note that the gelled product in the present invention includes all those which have started the gelling reaction by mixing the component (d), regardless of the degree of progress of the gelling reaction.

The pH of the aqueous coating material that forms a gel is not particularly limited as long as the gelation reaction can be initiated, but is usually 7 to 14. By setting the pH of the water-based paint to such a value, an appropriate reactivity can be obtained, particularly when (d-2) is used as the component (d).

The mixing of the water-based paint and the component (.d) may be carried out usually at room temperature, but it is also possible to heat the mixture to promote the gelation reaction.

Next, the gelled product is added to an aqueous dispersion medium and dispersed into flat particles. The timing of adding the gelled substance to the aqueous dispersion medium can be appropriately set, and may be immediately after mixing the aqueous paint and the component (d) or after leaving for a certain period of time. Here, as the aqueous dispersion medium, a part or the whole of the transparent paint can be used. When the gelled product is added to the aqueous dispersion medium, the aqueous resin may not be contained in the aqueous dispersion medium, and may be mixed in a later step.

In order to make the shape of the colored particles formed flat, the shape of the stirring blade, the size and position of the stirring blade with respect to the stirring tank, the rotation speed of the stirring blade, the viscosity of the water-based paint, the method of adding the gel, the transparent paint The viscosity or the like may be appropriately selected and adjusted. The particle size of the colored particles can be adjusted by the same method.

In the present invention, since the colored particles have a flat shape, a coating film having excellent smoothness can be formed. The minor axis and major axis of the colored particles are not particularly limited, but are usually from 0.01 to: L 0 mm, preferably from 0 :! To 5 mm, more preferably 0.7 to 2 mm.

When the gelled material is dispersed in the aqueous dispersion medium, a dispersion stabilizer can be used. Examples of such a dispersion stabilizer include a magnesium salt, a calcium salt, a barium salt, an aluminum salt, a sodium salt, a potassium salt, a borate and the like. In addition, a component that promotes the reaction of the unreacted portion in the colored particles can be mixed with the aqueous dispersion medium to further ensure gelation.

The pH of the aqueous dispersion medium is usually from 7 to 10, preferably from 7 to 9. In particular, when the component (d-2) is used, it is desirable to set the pH of the aqueous dispersion medium to such a range.

In the present invention, (d-1) can be further mixed after the gelled material is dispersed in the aqueous dispersion medium. In this case, the component (a-1) is used as the component (a).

By such a process, a reaction between the component (a-1) and the component (d-1) occurs on the surface layer of the colored particles, so that the suitability of the multi-color paint for roller coating and brush coating can be further improved. The coating film properties such as weather resistance and water resistance can also be improved.

The mixing amount of the (d-l) component is usually about 0.1 to 10% by weight based on the colored particles. The mixing of the (d-l) component may be carried out at room temperature, but it is also possible to heat it if necessary.

In order to obtain the composition of the present invention containing two or more kinds of colored particles having different hues, for example,

A method of producing a coating material in which monochromatic colored particles are dispersed and then mixing them; or

A method in which two or more gels having different hues are simultaneously or sequentially added to and dispersed in a dispersion medium;

Etc. may be adopted.

In the composition of the present invention, colored particles other than the flat colored gel particles may be mixed. Examples of such colored particles include crushed natural stones, colored aggregates, plastic pieces, rubber pieces, metal pieces, and inorganic mineral pieces.

In the composition of the present invention, known coating additives other than those described above may be appropriately used. Examples of such additives include a pigment dispersant, an antifoaming agent, a thickener, an ultraviolet absorber, an antioxidant, a fungicide, an antiseptic, a film-forming aid, an antifreeze, and the like. It is also possible to add a color pigment to the transparent paint as long as the sharpness of the coating film is not impaired. Use extender pigments etc. in aqueous paints that form colored particles It is also possible.

(Painting method)

The composition of the present invention can be applied to various uses such as, for example, for construction, building materials, civil engineering, woodwork, plastic products, metal products, and non-ferrous metal products. Specifically, for example, it is used as a surface decorative material for various base materials such as concrete, mortar, siding board, extruded molded board, gypsum board, perlite board, plywood, plastic board, metal board, glass, porcelain tile, etc. Is possible. The surface of these substrates may have been subjected to some kind of surface treatment (for example, a sealer, a serve acer, a filler, etc.), or may have a coating film already formed thereon, or may have a wallpaper applied thereto. You may.

In the present invention, it is desirable to form an undercoat layer with a colored matte undercoat paint (hereinafter, also simply referred to as "undercoat paint") before applying the multicolor paint composition. Such an undercoat layer has fine irregularities on the surface in the order of / m. These fine irregularities improve the coating workability of multi-color paints (especially when painting with a roller or when painting with a brush), making it possible to form a uniform and uniform pattern surface. . The degree of coloring in the undercoat paint may be such that the base material can be hidden.

Specifically, the luster of the undercoat paint in the present invention can be defined by its specular gloss. The specular gloss of the undercoat paint is usually 40 or less, preferably 20 or less, more preferably 10 or less. When the mirror gloss of the undercoat is high, it is difficult to apply the overcoat uniformly. The adjustment of the gloss of the undercoat paint can be appropriately performed depending on the type, particle diameter, mixing ratio, and the like of the extender described below.

The undercoat paint can be produced by mixing an aqueous resin, a color pigment, and an extender pigment.

As the aqueous resin, a water-dispersible resin and / or a water-soluble resin can be used. Examples of the type of resin include acrylic resin, urethane resin, vinyl acetate resin, silicon resin, fluorine resin, acrylic / butyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, polybutyl alcohol, and cellulose derivative. And one or more of these can be used. Such a water-dispersible resin or a water-soluble resin may have a property of causing a crosslinking reaction after the formation of a coating film. By having such a crosslinking reactivity, physical properties of the coating film such as water resistance and adhesion can be improved. In addition, when a cationic aqueous resin is used, when the base material contains lacquer, cannabis, or the like, leaching can be prevented.

Color pigments include, for example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, Bengala, molybdate orange, 1 permanent red, northern carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first toy yellow, benzimidazolone yellow, chrome green, kono noreto green, phthalocyan green, Ultramarine, navy blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, aluminum pigment, pearl pigment, and the like. The undercoat paint can be colored to a desired hue by using one or more of these coloring pigments.

The extender pigments include, for example, heavy calcium carbonate, cryolite, light calcium carbonate, white carbon, talc, kaolin, clay, porcelain clay, china clay, diatomaceous earth, barium powder, parium sulfate, sedimentable parium sulfate, Examples thereof include silica sand, silica stone powder, quartz powder, resin beads, glass beads, and hollow balloons, and one or more of these can be used. The average particle size of the extender is usually 0.1 to 500 ^ ιη, preferably 1 to 200 µm.

The mixing ratio of each component in the undercoat paint is such that the color pigment is 1 to 300 parts by weight (preferably 5 to 200 parts by weight) and the extender pigment is 5 to 100 parts by weight of the solid content of the aqueous resin. To 300 parts by weight (preferably 10 to 200 parts by weight).

In the undercoat paint, known paint additives may be appropriately used in addition to the components described above. Examples of such additives include a pigment dispersant, an antifoaming agent, a thickener, an ultraviolet absorber, an antioxidant, a fungicide, a preservative, a film-forming aid, an antifreeze, and the like.

The hue of the undercoat paint is not particularly limited, but is at least one kind of colored particles Color is desirable. By setting such a hue, it is possible to obtain a harmonious and highly aesthetic finish.

A roller, a brush, a trowel, a spray, or the like can be used to apply the undercoat paint. However, when used indoors, a roller or a brush is preferable in terms of coating workability, coating property, and the like. It can be diluted with water for painting. Coat-weight of the lower coating paint is usually 0. 05~0. 5 k gZm ^2.

Drying after application of the undercoat paint may be carried out at room temperature, but heating can also be carried out. The drying time is usually 0.5 to 5 hours. After the undercoat has dried, multicolor paints can be applied.

When painting multi-color paints, it is possible to use various types of coating equipment such as sprays, rollers, brushes, and irons. In particular, when the colored particles are derived from the components (a) to (d), a roller or a brush is suitable.

If the colored particles are derived from the components (a) to (d), a uniform finish can be obtained when different coating tools are used in combination for one coated surface. For this reason, even if repair is performed using a roller or a brush after spray coating, the finish can be made without discomfort.

It can be diluted with water for painting. The amount of water to be mixed may be appropriately set in consideration of the type of coating equipment, the state of the coating base, the temperature at the time of coating, and the like. The coating amount of the composition of the present invention is usually 0.2 to 1.6 kgZm ² , preferably 0.3 to 1.2 kg / m ² . In addition, drying after coating the composition of the present invention may be usually performed at room temperature, but heating may also be performed. Drying time is usually 1 to 5 hours.

The overcoat layer formed by the multicolor paint may be a continuous layer or a discontinuous layer. In particular, when a colored matte paint is used as the undercoat layer, it is possible to form a pattern surface without a sense of discomfort even if the overcoat layer does not necessarily completely cover the undercoat layer.

Example

Examples are shown below to further clarify the features of the present invention.

The following raw materials were used in the production of paint. Water-dispersible resin A: Acrylic resin emulsion (styrene-methyl methacrylate-2-ethylhexyl atalylate copolymer, minimum film formation temperature 3 ° C, pH 8.8, solid content 50% by weight )

'Water-dispersible resin B: Acrylic resin emulsion (Styrene monomethyl methacrylate-2-ethylhexyl acrylate copolymer, minimum film formation temperature 2 ° C, pH 6.2, solid content 50% by weight)

• Water-dispersible resin C: Carboxyl group-containing acryl-based resin emulsion (methyl methacrylate butyl acrylate-acrylic acid copolymer, minimum film formation temperature 0 ° C, pH 8.2, solid content 50% by weight)

• Water-dispersible resin D: Acrylic resin emulsion (styrene-butyl acrylate copolymer, minimum film-forming temperature 0 ° C, solid content 50% by weight)

• Water-soluble resin A: Hydroxyl cellulose powder

• Water-soluble resin B: Galata tomannan 3% by weight aqueous solution

• Pigment A: Heavy calcium carbonate (refractive index: 1.50, average particle size: 8 μπι)-Pigment ：: Silica powder (refractive index: 1.55, average particle size: 2111)

• Pigment C: Precipitating barium sulfate (refractive index: 1.64, average particle size: 4 μΐη) • Pigment D: silica powder (refractive index: 1.55, average particle size: 50 μm)

• Pigment E: Zinc oxide (refractive index 2.01, average particle size 0.2 / xm)

• Pigment F: Silica powder (refractive index: 1.55, average particle size: 150 μm)

• White pigment liquid A: titanium oxide 60% by weight dispersion (dispersant: carboxylic acid-based dispersant, molecular weight 1800)

• White pigment liquid B: 60% by weight dispersion of titanium oxide (dispersant: cationic polymer dispersant (alkylamine adduct of alkylamine, molecular weight 15000, HLB 8))

• Black pigment liquid A: 15% by weight black iron oxide dispersion (dispersant: carboxylic dispersant, molecular weight 1800)

• Black pigment liquid B: Black iron oxide 15% by weight dispersion (Dispersant: Thion polymer dispersant (alkylamine amine adduct of alkylamine, molecular weight 15000, HLB 8)) • Reactive compound A: Butoxy modified product of tetramethoxysilane condensate • Reactive compound B: Tetramethoxysilane condensate

* Reactive compound C: 2,2-bishydroxymethylpthano monolithris [3- (1-aziridyl) propionate]

• H regulator: ammonia water

• Antifoam: Silicone antifoam

[Test Example 1]

(Manufacture of colorful paints)

Paint composition 11 A

First, 200 parts by weight of the water-dispersible resin A is charged into a container, and while stirring at a rotation speed of the stirring blade of 1800 rpm, 3 parts by weight of the water-soluble resin A, 20 parts by weight of the pigment A, and the defoamer 1 By weight, 250 parts by weight of water and 250 parts by weight of water were uniformly mixed to produce 11 A of a transparent paint. This transparent paint 1-A had a pH of 8.0 and a specular gloss of 8.

Next, 90 parts by weight of the water-dispersible resin A is charged into another container, and while stirring at a rotation speed of the stirring blade of 1800 rpm, 180 parts by weight of the water-soluble resin B and the white pigment liquid 90 are mixed. By weight, 5 parts by weight of an antifoaming agent, 80 parts by weight of water, and 5 parts by weight of a reactive compound A were uniformly mixed to produce a white water-based paint 11A. The pH of this water-based paint 1-A was 9.5.

8 parts by weight of a 5% by weight aqueous solution of ammonium borate as a dispersion stabilizer was added to 1474 parts by weight of the above-mentioned transparent paint, and the mixture was uniformly mixed at a rotation speed of the stirring blade of 900 rpm and then further stirred. By gradually adding and dispersing 450 parts by weight of the aqueous paint 1_A while continuing the above, a paint composition 11A in which flat white particles of 0.8 to 1.2 mm were dispersed was obtained.

Paint composition 11 B

Except for using the raw materials at the mixing ratios shown in Table 1, paints were prepared in the same manner as the paint composition 11A, and the coatings in which 1.0 to 1.6 mm flat gray particles were dispersed were used. Material composition 11B was obtained.

Paint composition 11 C A coating material was prepared in the same manner as in the coating composition 11A except that each raw material was used in the mixing ratio shown in Table 1, and the coating material in which 0.8 to 1.2 mm flat black particles were dispersed was used. Material composition 11C was obtained.

Paint composition 11D

Except for using the raw materials at the mixing ratios shown in Table 1, a paint was produced in the same manner as in the paint composition 11A, and the 0.8 to 1.6 mm flat gray particles were dispersed. Material composition 11D was obtained.

Paint composition 11 E

A coating material was prepared in the same manner as in coating composition 11A except that each raw material was used at the mixing ratio shown in Table 1, and a coating material in which 0.8 to 1.2 mm flat black particles were dispersed was prepared. Composition 11 was obtained.

Paint composition 11 F

Except for using the raw materials at the mixing ratios shown in Table 1, a coating was produced in the same manner as the coating composition 11A, and the coating in which 0.8 to 1.4 mm flat gray particles were dispersed was used. Material composition 11F was obtained.

Paint composition 11 G

Except that each raw material was used in the mixing ratio shown in Table 1, a paint was produced in the same manner as the paint composition 11A, and 0.8 to 1.2 mm flat black particles were dispersed. This gave 11 G of the coating composition.

Paint composition 11 H

Except for using the raw materials at the mixing ratios shown in Table 1, a paint was prepared in the same manner as the paint composition 11A, and a coating in which flat gray particles of 1.0 to 1.8 mm were dispersed. Material composition 11H was obtained.

Coating composition 11

A coating material was prepared in the same manner as for coating composition 11A except that the raw materials were used in the mixing ratios shown in Table 1, and a coating in which flat black particles of 1.2 to 1.6 mm were dispersed. Material composition 11 was obtained.

Coating composition 11 .T

Same as coating composition 11A except that each raw material was used in the mixing ratio shown in Table 1. A coating composition was prepared by the method described above to obtain a coating composition 11 J in which flat gray particles of 0.8 to 1.4 mm were dispersed.

Paint composition 11 K

A coating material was prepared in the same manner as in the coating composition 11A except that each raw material was used in the mixing ratio shown in Table 1, and the coating material in which 0.8 to 1.2 mm flat black particles were dispersed was used. The composition 1-K was obtained.

Paint composition 11 L

Except for using the raw materials at the mixing ratios shown in Table 1, a paint was prepared in the same manner as the paint composition 11A, and the coating was performed with 1.0 to 1.8 mm flat gray particles dispersed. One liter of the composition was obtained.

Paint composition 11 M

Except for using each raw material at the mixing ratio shown in Table 1, a paint was manufactured in the same manner as the paint composition 11A, and a coating in which flat black particles of 1.0 to 1.6 mm were dispersed. Material composition was obtained.

Paint composition 11 N

Except for using the raw materials at the mixing ratios shown in Table 1, paints were prepared in the same manner as the paint composition 11A, and the coatings in which 1.0 to 1.6 mm flat gray particles were dispersed were used. Material composition 11N was obtained.

Paint composition 11 O

A coating material was prepared in the same manner as in the coating composition 11A except that the raw materials were used in the mixing ratio shown in Table 1, and the coating material in which 0.8 to 1.4 mm flat black particles were dispersed was prepared. Material composition 11 O was obtained.

1-A 1-Bic 1-D 1-E 1-F 1- G 1: H '1-1-1-J 1-1-L 1-M 1-N 1-0 Water dispersible resin A 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 Water soluble resin A 3 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Pigment 20 Transparent pigment D 35 35

Light

Pigment E 35 35

Defoamer 1 1 1 1 1 1 1 1 1 1 1 1-1 1 1 Water 250 380 380 380 380 380 380 380 380 380 380 380 380 380 380 380 Dispersion stabilizer 8 10 8 10. 8 10 8 10 8 10 8 10 8 10 8 o.o, ts.

, / Sentence 5

be

h- ¹ Water dispersible resin A 90 85 100 85 100 85 100 85 100 85 100-85 100 Water dispersible resin: B 85 100

Water-soluble resin B 180 250 200 250 200 250 200 250 200 250 200 250 200 250 200 White face difficulty A 90 50 50 50 50 50 50 White face Night B 50

Water Black face S A 50 100 50 100 50 100 50 100 50 100 50 100 Sex Black face B 50 100

Family pH regulator 4 4 4 4 4 4 Defoamer 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Water 80 50 70 50 70 50 70 50 70 50 70 50 70 50 70 Anti-compound A 5 10 25 10 25 10 25 10 25 10 25 Reactive compound B 10 25

H 9.5 9.2 11.5 9.0 11.2 9.0 11.4 9.1 11.2 6.4 6.8 9.2 11.5 9.2 11.5 All values in the table are by weight except for specular gloss and pH

(Example 11)

A slate plate coated with a gray sealer in advance was coated with a multi-colored paint obtained by mixing the paint composition 11A and the paint composition 1-B at a weight ratio of 50:50 with a sand-bone roller. Was applied at a coating amount of 0.6 kg Zm ² using, dried at room temperature for 24 hours, and the state of the coating film was observed. In Example 1-1, a mixture of white and gray was able to form a smooth and highly visible pattern coating film. No abnormalities in the colored particles were observed.

(Example 1-2)

As a multicolor paint, except that the paint composition 11 A, the paint composition 11 B, and the paint composition 11 C were mixed in a weight ratio of 80: 10: 10 Example 11 Coating was performed in the same manner as in Example 1.

In Examples 1-2, white, gray, and black were mixed, and a smooth, highly visible pattern coating film could be formed. No abnormality of the colored particles was observed.

(Example 13)

Coating was carried out in the same manner as in Example 11-11, except that a paint composition 11D and a coating composition 11E were mixed at a weight ratio of 50:50 as the multicolor paint. went.

In Examples 13 and 13, gray and black were mixed, and a smooth and clear pattern coating film could be formed. No abnormality of the colored particles was observed.

(Examples 1-4)

The same as Example 11 except that the paint composition 11F and the paint composition 11G were mixed in a weight ratio of 50:50 as the multicolored paint. Painted.

In Examples 1-4, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. However, gray and black bleeding occurred from the colored particles.

(Example 1-5)

Same as Example 11-1 except that a paint composition in which paint composition 11H and paint composition 11I were mixed at a weight ratio of 50:50 was used as the multicolored paint. Was painted.

In Examples 1 to 5, a pattern coating film having high clarity and a mixture of gray and black could be formed. However, as compared with Example 1-1, irregularities became noticeable.

(Example 1-6)

The same as Example 11 except that the paint composition 11-J and the paint composition 11-K were mixed in a weight ratio of 50:50 as the multicolor paint. Painted.

In Examples 1 to 6, gray and black were mixed, and a pattern coating film having high smoothness and high clarity could be formed. However, gray and black bleeding occurred from the colored particles.

(Example 1-7)

The same as in Example 11 except that a multi-pattern paint used was a paint composition in which 11 L of the paint composition and 11 M of the paint composition were mixed at a weight ratio of 50:50. Painted.

In Example 117, a smooth pattern coating film in which gray and black were mixed was able to be formed. However, the finished image was slightly inferior to Example 11 in sharpness. (Reference Example 1-1)

The same as Example 11 except that a paint composition in which the paint composition 11 N and the paint composition 11 O were mixed in a weight ratio of 50:50 was used as the multicolored paint. Painted.

In Reference Example 1-11, the entire coating film became whitish, and a pattern coating film with high clarity could not be formed.

[Test Example 2]

(Manufacture of colorful paints)

Paint composition 2—A

First, 200 parts by weight of the water-dispersible resin A was charged into a container, and 4 parts by weight of the water-soluble resin A and 35 parts by weight of the pigment B were stirred while stirring at a rotation speed of the stirring blade of 180 rpm. And 1 part by weight of an antifoaming agent and 380 parts by weight of water Thus, Transparent Paint 2-A was produced. The pH of the transparent paint 2-A was 8.1 and the specular gloss was 5.

Next, 85 parts by weight of the water-dispersible resin C was charged into another container, and while stirring at a rotation speed of the stirring blade of 1800 rpm, 250 parts by weight of the water-soluble resin B and the white pigment liquid A were mixed. 50 parts by weight of black pigment liquid A, 5 parts by weight of antifoaming agent, 50 parts by weight of water, and 3 parts by weight of reactive compound C are uniformly mixed with 50 parts by weight of a white water-based paint 2-A Was manufactured. The pH of this water-based paint 2-A was 8.9. 10 parts by weight of a 5% by weight aqueous solution of ammonium borate as a dispersion stabilizer was added to 620 parts by weight of the above transparent paint 2-A, and the mixture was uniformly mixed at a rotation speed of the stirring blade of 900 rpm, followed by further stirring. By continuously adding and dispersing 3 parts by weight of the aqueous paint 2-A49 while continuing to obtain a paint composition 2-A in which 0.7 to 1.2 mm flat gray particles are dispersed.

Paint composition 2—B

A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and a coating material in which 0.8 to 1.6 mm flat black particles were dispersed was prepared. The composition 2—B was obtained.

Paint composition 2—C

A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and a coating material in which flat gray particles of i.0 to 1.6 mm were dispersed. Material composition 2-C was obtained.

Paint composition 2—D

A coating material was prepared in the same manner as in coating composition 2-A except that the raw materials were used in the mixing ratio shown in Table 2, and the coating material in which 0.8 to 1.4 mm flat black particles were dispersed was used. Material composition 2-D was obtained.

Paint composition 2—E

Except for using the raw materials at the mixing ratios shown in Table 2, a paint was produced in the same manner as in paint composition 2-A, and a coating in which flat gray particles of 1.0 to 1.6 mm were dispersed. The composition 2—E was obtained.

Paint composition 2—F A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and the coating material in which 0.8 to 1.5 mm flat black particles were dispersed was used. The composition 2-F was obtained.

In the production of the coating compositions 2-E and F, a mixture of the water-based paint and the reactive compound C was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed.

Paint ¾a composition 2— G

A coating material was prepared in the same manner as in coating composition 2-A except that the raw materials were used in the mixing ratio shown in Table 2, and the coating material in which 0.8 to 1.4 mm flat gray particles were dispersed was used. The composition 2—G was obtained.

Paint composition 2—H, paint was prepared in the same manner as paint composition 2—A, except that each raw material was used in the mixing ratio shown in Table 2. The coating composition 2-H in which the black particles were dispersed was obtained.

In the production of the coating compositions 2-G and H, a mixture of the water-based paint and the reactive compound A was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed. '' Coating composition 2-I

Except for using the raw materials at the mixing ratios shown in Table 2, a paint was produced in the same manner as in paint composition 2-A, and a coating in which flat gray particles of 1.0 to 1.6 mm were dispersed. The composition 2—I was obtained.

Paint composition 2—J

A coating material was prepared in the same manner as in coating composition 2-A except that the raw materials were used in the mixing ratio shown in Table 2, and the coating material in which 0.8 to 1.5 mm flat black particles were dispersed was used. The composition 2—J was obtained.

Paint composition 2—K

A coating material was prepared in the same manner as in coating composition 2'-A, except that each raw material was used in the mixing ratio shown in Table 2, and 0.8 to 1.4 mm flat gray particles were dispersed. Coating composition 2-K was obtained. Paint composition 2— L

A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and a coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. The composition 2—L was obtained.

Paint composition 2—M

A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and a coating material in which 0.8 to 1.5 mm flat gray particles were dispersed was used. The composition 2—M was obtained.

Paint composition 2—N

A coating material was prepared in the same manner as in coating composition 2-A except that each raw material was used in the mixing ratio shown in Table 2, and a coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. The composition 2—N was obtained.

2-A 2-B 2-C 2-D 2-E 2-F 2-G 2-H 2- 1 2-J 2-K 2-L 2-M 2-N

Water dispersible resin A 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200

Water-soluble shelf 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

Pigment B 35 35 35 35 35 35 35 35 35 35 35

Pigment. 35 35

Pigment Ε 35 35

Light

Shelf 1 1 1 1 1 1 1 1 1 1 1 1 1 1

Fee

Water 380 380 380 380 380 380 380 380 380 380 380 380 380 380

Dispersion trend 10 8 10 8 10 8 10-8 10 8 10 8 10 8

H 8.1 8.0 8.1 8.0 8.1 8.0 8.1 8.0 8.1 8.1 8.1 8.0 8.2 8.1

Specular gloss 5 5 5 5 5 5 5 5 4 4 5 5 72 72

Water dispersible resin A----------85 100---to Water dispersible resin C 85 100 85 100 85 100 85 100 85 100---85 "100

Three

Mizunada Resin B 250 200 250-200 250 200 250 200 250 200 250 200 250 200

White face fiber A 50-------50-50-50-White pigment liquid: B-50-50-50-------Water Black face fiber A 50 1Q0------50 100 50 100 50 100

i Black face B 50 100 50 100 50 100

Fee pH transposition 4 4

Defoamer '5 5 5' 5 5 5 5 5 5 5 5 5 5 5

Water 50 70 50 '-70 50 70 50 70 50 70 50 70 50 70

Reactive compound A 10 25

Reactivity 3 3 3 3 3 3 3. 3 3 3

H 8.9 8.7 8.9 8.7 8.9 8.7 9.0 11 3 8.9 8.7 9.0 11.4 8.9 8.7

Reactive compound C 3 1 3 1

PH: All figures in the table are parts by weight except for specular gloss

锵 2 (Example 2-1)

A slate plate coated with a gray sealer in advance was coated with a multi-colored paint in which the paint composition 2—A and the paint composition 2—B were mixed at a weight ratio of 50:50. Was applied at a coating amount of 0.6 kg Zm ² using, dried at room temperature for 24 hours, and the state of the coating film was observed. In Example 2-1, gray and black were mixed, and a smooth and highly visible patterned film could be formed. No abnormalities in the colored particles were observed.

(Example 2-2)

The coating was performed in the same manner as in Example 2-1 except that the paint composition 2-C and the paint composition 2-D were mixed at a weight ratio of 50:50 as the multicolor paint. went.

In Example 2-2, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. No abnormality of the colored particles was observed.

(Example 2-3)

The coating was carried out in the same manner as in Example 2-1 except that a paint composition 2—E and a paint composition 2—F were mixed at a weight ratio of 50:50 as the multicolor paint. went.

In Examples 2-3, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. No abnormality of the colored particles was observed.

(Example 2-4)

The coating was carried out in the same manner as in Example 2-1 except that a paint composition 2—G and a paint composition 2—H were mixed in a weight ratio of 50:50 as the multicolor paint. went.

In Example 2-4, a mixture of gray and black was formed, and a smooth and highly visible pattern coating film could be formed. No abnormality of the colored particles was observed.

(Example 2 _ 5)

As in Example 2-1 except that a paint composition in which the paint composition 2—I and the paint composition 2—J were mixed in a weight ratio of 50:50 was used as the multicolor paint. Painted. In Examples 2-5, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. However, the finished image was slightly inferior to Example 2-1 in sharpness.

(Example 2-6)

Same as Example 2-1 except that a paint composition in which a paint composition 2—K and a paint composition 2—L were mixed in a weight ratio of 50:50 was used as a multicolor paint. Was painted.

In Examples 2-6, a mixture of gray and black was formed, and a smooth and highly visible pattern coating film could be formed. However, gray and black bleeding occurred from the colored particles.

(Reference example 2-1)

As in Example 2-1 except that a paint composition in which paint composition 2—M and paint composition 2—N were mixed at a weight ratio of 50:50 was used as the multicolor paint. Painted. '

In Reference Example 2-1, the entire coating film became whitish, and a pattern coating film with high sharpness could not be formed.

[Test Example 3]

(Manufacture of colorful paints)

Paint composition 3—A

200 parts by weight of the water-dispersible resin A was charged into the container, and while stirring at a rotation speed of the stirring blade of 180 rpm, 3 parts by weight of the water-soluble resin A and 1 part by weight of the defoamer were added. Transparent paint 3-A was produced by uniformly mixing 250 parts by weight of water. The pH of this transparent paint 3_A was 8.1.

Next, 90 parts by weight of the water-dispersible resin A was charged into another container, and 180 parts by weight of the water-soluble resin B was mixed with white while stirring at a rotation speed of the stirring blade of 180 rpm. By mixing uniformly 90 parts by weight of the pigment liquid, 5 parts by weight of the defoamer, and 80 parts by weight of water, a white water-based paint 3-A was produced. The pH of this water-based paint 3-A was 9.5.

Ammonium borate as a dispersion stabilizer for the above transparent paint 3—A 454 parts by weight After adding 8 parts by weight of a 5% by weight aqueous solution of lithium and uniformly mixing the stirring blades at a rotation speed of 900 rpm, while continuing stirring, the water-based paint 3—A445 parts by weight and the reactive compound A 5 By slowly adding and dispersing the mixture with parts by weight, a coating composition 3-A in which 0.8 to 1.2 mm flat white particles were dispersed was obtained. Paint composition 3—B

A coating material was prepared in the same manner as in coating composition 3-A except that the raw materials were used in the mixing ratios shown in Table 3, and the coating material in which flat gray particles of 1.0 to 1.6 mm were dispersed. A composition 3—B was obtained.

Paint composition 3—C

A coating material was prepared in the same manner as in coating composition 3-A except that the raw materials were used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.2 mm flat black particles were dispersed was used. The composition 3—C was obtained.

Paint composition 3—D

A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and a coating material in which 0.8 to 1.6 mm flat gray particles were dispersed was used. The composition 3—D was obtained.

Paint composition 3—E

A coating material was prepared in the same manner as in coating composition 3-A except that the raw materials were used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.2 mm flat black particles were dispersed was used. The composition 3—E was obtained.

Paint composition 3—F

A coating material was prepared in the same manner as for coating composition 3-A except that the raw materials were used at the mixing ratios shown in Table 3, and the coating material in which flat gray particles of 1.0 to 1.8 mm were dispersed. The composition 3—F was obtained.

Paint composition 3—G

A coating material was prepared in the same manner as in coating composition 3-A except that the raw materials were used in the mixing ratio shown in Table 3, and the coating material in which 1.2 to 1.6 mm flat black particles were dispersed was used. The composition 3—G was obtained.

Paint composition 3—H A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.5 mm flat gray particles were dispersed was used. The composition 3—H was obtained.

Paint composition 3—I

A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. The composition 3—I was obtained. '

Paint composition 3—J

A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and a coating material in which flat gray particles of 1.2 to 1.8 mm were dispersed. The composition 3—J was obtained.

Paint composition 3—K

A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. Material composition 3—K was obtained.

In the production of the coating compositions 3_J and K, a mixture of the water-based paint and the reactive compound C was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed.

Paint composition 3—L

A coating material was prepared in the same manner as in coating composition 3-A, except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.6 mm flat gray particles were dispersed was used. Material composition 3—L was obtained.

Paint composition 3—M

A coating material was prepared in the same manner as in coating composition 3-A except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.4 mm flat black particles were dispersed was used. The composition 3—M was obtained.

In the production of the coating compositions 3-L and M, a mixture of the water-based paint and the reactive compound A was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed. Paint composition 3—N

A coating material was prepared in the same manner as in coating composition 3-A except that the raw materials were used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.4 mm flat gray particles were dispersed was used. The composition 3_H was obtained.

Paint composition 3—O

A coating material was prepared in the same manner as in coating composition 3-A, except that each raw material was used in the mixing ratio shown in Table 3, and the coating material in which 0.8 to 1.2 mm flat black particles were dispersed was used. The composition 3—I was obtained.

o A. d length o) o Ji o Lr Water dispersible resin A 200 200 200 200 200 200 200 Water resin A 3 4 4 4 4 4 4 Defoamer 1

Ming 1 1 1 1 1 1 Water 250 380 380 380 380 380 380 Fee

Dispersion stabilizer 8.10 8 10 8 10 8 pH 8.1 8.2 8.2 8.2 8.2 8.2 '8.2 Ice dispersible resin A 90 85 100 85 100 85 100 Dispersible resin C

Water-soluble resin B 180 250 200 250 200 250 200 White pigment liquid A 90 50 50

Black pigment liquid A 50 100 50 100 Water Black color liquid B 50 100

Sex

PH adjuster 4 4 4 '

Defoamer 5 5 5 5 5 5 5 Water 80 '50 70 50 70 50 70 Reactive compound A 5 10 25 10 25

Reactive compound B. 10 25 Reactive compound C

PH 9.5 9.2 11.5 9.0 11.2 9.1 11.2 Reactive compound C

All figures in the table except for pH are parts by weight

Two

All figures in the table except for pH are parts by weight

(Example 3-1)

A slate plate coated with a gray sealer in advance was coated with a multi-colored paint obtained by mixing paint composition 3—A and paint composition 3—B at a weight ratio of 50:50. Was applied at a coating amount of 0.6 kg Zm ² using, dried at room temperature for 24 hours, and the state of the coating film was observed. In Example 3-1, white and gray were mixed, and a pattern coating film having high smoothness and high visibility could be formed. No abnormalities in the colored particles were observed.

(Example 3-2)

As a multi-color paint, except that paint composition 3-A, paint composition 3-B and paint composition 3-C were mixed at a weight ratio of 80:10:10, Coating was performed in the same manner as in Example 3-1.

In Example 3-2, a mixture of white, gray, and black was able to form a smooth, highly visible pattern coating film. No abnormality of the colored particles was observed.

(Example 3-3)

The coating was performed in the same manner as in Example 3-1 except that a paint composition 3-D and a paint composition 3-E were mixed at a weight ratio of 50:50 as the multicolored paint. went.

In Example 3-3, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. No abnormality of the colored particles was observed.

(Example 3-4)

As in Example 3-1 except that a paint composition in which paint composition 3-F and paint composition 3-G were mixed at a weight ratio of 50:50 was used as the colorful pattern paint. Painted.

In Example 3-4, it was possible to form a pattern coating film with high clarity in which gray and black were mixed. However, as compared with Example 3-1, the unevenness became slightly noticeable.

(Example 3-5)

Coating was performed in the same manner as in Example 3-1 except that a paint composition 3—H and a paint composition 3—I were mixed in a weight ratio of 50:50 as the multi-colored paint. Was done.

In Example 3-5, a mixture of gray and black was able to form a smooth and clear pattern coating film. No abnormality of the colored particles was observed.

(Example 3-6)

The coating was carried out in the same manner as in Example 3-1 except that a paint composition 3—J and a paint composition 3—K were mixed at a weight ratio of 50:50 as the multicolor paint. went.

In Example 3-6, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. No abnormality of the colored particles was observed.

(Example 3-7)

The coating was performed in the same manner as in Example 3-1 except that a paint composition 3—L and a paint composition 3—M were mixed at a weight ratio of 50:50 as the colorful pattern paint. went.

In Example 3-7, a mixture of gray and black was able to form a smooth and highly visible pattern coating film. No abnormality of the colored particles was observed.

(Reference example 3-1)

As in Example 3-1 except that a paint composition in which paint composition 3-N and paint composition 3-O were mixed at a weight ratio of 50:50 was used as the multicolor paint. After painting, gray and black bleeding occurred from the colored particles.

[Test Example 4]

(Manufacture of undercoat paint)

Undercoat paint 41 A

A stirrer was prepared by mixing 40 parts by weight of white pigment liquid A, 30 parts by weight of black pigment liquid A, 8 parts by weight of pigment F, and 1 part by weight of defoamer with respect to 200 parts by weight of water-dispersible resin D. The resulting mixture was uniformly mixed to produce a gray undercoat paint 41A. The specular gloss of this undercoat paint 41A was 3.0.

Undercoat paint 41 B

To 200 parts by weight of water-dispersible resin D, 200 parts by weight of white pigment liquid A, 15 parts by weight of black pigment liquid A, 5 parts by weight of pigment F, and 1 part by weight of defoamer were added to a stirrer. And evenly By mixing, a gray undercoat paint 41-B was produced. The specular gloss of the undercoat paint 4-B was 35.

Undercoat paint 41 C

By mixing uniformly 200 parts by weight of the white pigment liquid A, 10 parts by weight of the black pigment liquid A, and 1 part by weight of the defoamer with respect to 200 parts by weight of the water dispersible resin D The gray primer coat 41-C was manufactured. The undercoat paint 41-C has a specular gloss of 75, which is particularly important.

(Manufacture of colorful paints)

Paint composition 41 A

First, 200 parts by weight of the water-dispersible resin A is charged into a container, and 3 parts by weight of the water-soluble resin A and 20 parts by weight of the pigment B are stirred while stirring at a rotation speed of the stirring blade of 180 rpm. And 1 part by weight of an antifoaming agent and 250 parts by weight of water were uniformly mixed to produce Transparent Paint 41A. The pH of this transparent coating composition 41A was 8.2 and the specular gloss was 7.

Next, 90 parts by weight of the water-dispersible resin A was charged into another container, and 180 parts by weight of the water-soluble resin B was mixed with white while stirring at a rotation speed of the stirring blade of 180 rpm. 90 parts by weight of a pigment liquid A, 5 parts by weight of an antifoaming agent, 80 parts by weight of water, and 5 parts by weight of a reactive compound A were uniformly mixed to produce a white water-based paint 41A. _c The pH of this water-based paint 41A was 9.5.

8 parts by weight of a 5% by weight aqueous solution of ammonium borate as a dispersion stabilizer were added to 474 parts by weight of the above-mentioned transparent coating material A4, and the mixture was uniformly mixed at a rotation speed of the stirring blade of 900 rpm. Thereafter, while continuing stirring, 450 parts by weight of the water-based coating material A was gradually added and dispersed, whereby a coating composition having 0.8 to 1.4 mm flat white particles dispersed therein was dispersed. A got. '

Paint composition 41 B

A coating composition was prepared in the same manner as the coating composition 41A except that each raw material was used in the mixing ratio shown in Table 4, and the flat gray particles of 1.0 to 1.6 mm were dispersed. Paint Composition 41-B was obtained.

Paint composition 41 C A coating composition was prepared in the same manner as for coating composition 41A except that each raw material was used in the mixing ratio shown in Table 4, and 0.8 to 1.2 mm flat black particles were dispersed. The obtained coating composition 41C was obtained.

Paint composition 41D

A coating composition was prepared in the same manner as the coating composition 41A except that the raw materials were used in the mixing ratio shown in Table 4, and 0.8 to 1.4 mm flat gray particles were dispersed. The obtained coating composition 41-D was obtained.

Paint composition 41 E

A coating composition was prepared in the same manner as for coating composition 41A except that each raw material was used in the mixing ratio shown in Table 4, and 0.8 to 1.2 mm flat black particles were dispersed. Paint Composition 41-E was obtained.

Paint composition 41 F

A coating composition was prepared in the same manner as the coating composition 4.1A except that each raw material was used in the mixing ratio shown in Table 4, and flat gray particles of 1.0 to 1.8 mm were produced. A dispersed coating composition 4-F was obtained.

Paint composition 41 G

A coating composition was prepared in the same manner as for coating composition 41A except that each raw material was used at the mixing ratio shown in Table 4, and a flat black particle of 1.2 to 1.6 mm was produced. 41 G of the dispersed coating composition was obtained.

Paint composition 41 H

A coating composition was prepared in the same manner as the coating composition 41A except that the raw materials were used in the mixing ratio shown in Table 4, and 0.8 to 1.4 mm flat gray particles were dispersed. The obtained coating composition 41H was obtained.

Paint composition 41 I

A coating composition was prepared in the same manner as for coating composition 41A except that each raw material was used in the mixing ratio shown in Table 4, and 0.8 to 1.2 mm flat black particles were dispersed. The obtained coating composition 41-I was obtained.

Paint composition 41

Same as coating composition 41-A, except that each raw material was used in the mixing ratio shown in Table 4. The coating composition was produced by the method described in the above to obtain a coating composition 41-J in which flat gray particles of 1.0 to 1.8 mm were dispersed.

Paint composition 41 K

A coating composition was prepared in the same manner as the coating composition 41A except that each raw material was used at the mixing ratio shown in Table 4, and flat black particles of 1.0 to 1.6 mm were dispersed. The obtained coating composition 41K was obtained.

Paint composition 41 L

A coating composition was prepared in the same manner as the coating composition 41A except that the raw materials were used in the mixing ratios shown in Table 4, and the flat gray particles of 1.2 to 2.Omm were dispersed. 41 L of coating composition were obtained.

Paint composition 41 M

A coating composition was prepared in the same manner as the coating composition 41A except that each raw material was used at the mixing ratio shown in Table 4, and flat black particles of 1.0 to 1.6 mm were dispersed. Thus, 41 M of the obtained coating composition was obtained.

4-A 4-B 4-C 4-D 4-E 4-F 4-G 4-H 4- 1 4-J 4- 4--L 4-M

Furnace resin A 200 200 '200 200 200 200 200 200 200 200 200 200 200 200

Permanent resin A 3 '4 4 4 4 4 4 4 4 4 4 4 4

Pigment B 20 35 35 35 35 35 35 35 35

Pigment D 35 35

Transparent

Antifoam 1 1 1 1 1 1 1 1 1 1 1 1 1

Water 250 380 380 380 380 380 380 380 380 380 380 380 380

Dispersion stabilizer 8 10 8 10-8 10-8 10 8 10 8 10 8

H 8.2 8.1 8.1 8.1 8.1 8.1 '8.1 8.1 8.1 8.1 8.1 8.2 8.2 8.2

Specular gloss 7 5 5 5 5 5 5 5 5 4 4 86 86

Water dispersible resin A 90 85 100 85 100 85-100--85 100 85 100

o t

Water dispersible resin B-------85 100----Water soluble resin B 180 250 200 250 200 250 200 250 200 '250 200 250 200

White.Color face Fiber A 90 50 50 50 50 50 60

Black pigment liquid A 50 100 50 100 50 100 50 100 50 100 50 100

water

PH adjuster 4 4 4 4 4

5 5 5 5 5-5 5 5 5 5 5 δ

Water .80 50 70 50 70 50 70 50 70 50 70 50 70

Anti-striking compound A 5 10 25 10 25 10 25 10 25

Reactivity "ib compound B 10 25

'5 H 9.5 9.2 11-5' 9.0 11.4 9,1 11.2 6,4 6.8 9.2 11.5 9.2 11.5

'All values in the table are parts by weight except for specular gloss and ρ Η

¾4 (Example 4-1)

Undercoat paint 41 A was applied to the slate plate using a wall roller at a coating amount of 0.3 kg / m ² .

After drying at room temperature for 2 hours, the amount of the multicolored paint obtained by mixing the paint composition 4-1A and the paint composition 4-1B at a weight ratio of 50:50 was applied using a sand roller. 0. was painted with a 6 kg Zm ^2. Here, the state of the colored particles of the multicolored paint was observed, but no particular abnormality was observed.

Then, after drying at room temperature for 24 hours, the state of the coating film was observed. Example 4 The coating film formed in Example 11 had a smooth pattern of white and gray mixed, and had a uniform and uniform finish.

(Example 4-2)

As the multicolored paint, except that a paint in which the paint composition 41A, the paint composition 41B, and the paint composition 41C were mixed at a weight ratio of 80:10:10 was used. The coating was performed in the same manner as in Example 4-11.

In Example 4_2, no abnormality of the colored particles was observed. Further, the formed coating film had a smooth pattern in which white, gray and black were mixed, and had a uniform and uniform finish.

(Example 4-1-3)

The coating was performed in the same manner as in Example 4-11, except that a paint in which the paint composition 41-D and the paint composition 41-E were mixed at a weight ratio of 50:50 was used as the multicolor paint. went. 'The coating film formed in Examples 43 was a smooth pattern in which gray and black were mixed. However, gray and black bleeding occurred from the colored particles.

(Example 4-1-4)

The coating was performed in the same manner as in Example 4_1 except that a paint in which the paint composition 41-F and the paint composition 41-G were mixed at a weight ratio of 50:50 was used as the multi-pattern paint. went.

In Examples 4 to 14, no abnormality of the colored particles was observed. Further, the formed coating film was a pattern in which gray and black were mixed. In comparison with Example 4-11, The unevenness has become noticeable.

(Example 4-1-5)

The coating was performed in the same manner as in Example 4-11, except that a paint in which the paint composition 41H and the paint composition 41I were mixed in a weight ratio of 50:50 was used as the multi-color paint. went. '

The coating film formed in Examples 4 to 5 had a smooth pattern in which gray and black were mixed. However, gray and black bleeding occurred from the colored particles.

(Example 4-1-6)

Coating was performed in the same manner as in Example 41-11, except that undercoat paint 4_B was used as the undercoat paint.

The coating film formed in Examples 4 to 16 had a smooth pattern in which gray and black were mixed. However, when the multi-color paint was applied by roller, the colored particles were applied slightly unevenly, resulting in unevenness in a part of the formed coating film.

(Example 4-1 7)

Coating was carried out in the same manner as in Example 4-11, except that a paint in which the paint composition 41-J and the paint composition 41-K were mixed in a weight ratio of 50:50 was used as the multicolor paint. went.

The coating film formed in Examples 417 was a smooth pattern in which gray and black were mixed. However, the finished image was slightly inferior to Example 4-1 in sharpness.

(Reference Example 4-1)

Except that undercoat paint 41-B was used as undercoat paint and that paint composition 41-L and paint composition 4-M were mixed at a weight ratio of 50:50 as a multi-color paint. The coating was performed in the same manner as in Example 4-11.

In Reference Example 411, when the multi-color paint was applied by roller, the colored particles were applied unevenly, resulting in significant unevenness of the formed coating film.

(Reference Example 4-2)

Coating was performed in the same manner as in Example 41-11, except that undercoat paint 41C was used as the undercoat paint.

In Reference Example 4-11, the colored particles were uneven when the multi-color paint was applied by roller. It was in the state of being applied immediately, and the formed coating film was significantly uneven.

[Test Example 5]

(Manufacture of undercoat paint)

Primer paint 5—A

A stirrer was prepared by mixing 40 parts by weight of white pigment liquid A, 30 parts by weight of black pigment liquid A, 8 parts by weight of pigment F, and 1 part by weight of defoamer with respect to 200 parts by weight of water-dispersible resin D. The mixture was uniformly mixed to prepare a gray undercoat paint 5-A. The specular gloss of the undercoat paint 5-A was 3.0.

Primer paint 5—B

To 200 parts by weight of water-dispersible resin D, 200 parts by weight of white pigment liquid A, 15 parts by weight of black pigment liquid A, 5 parts by weight of pigment F, and 1 part by weight of defoamer were added to a stirrer. By mixing uniformly, a gray undercoat paint 5-B was produced. The specular gloss of this undercoat paint 5-B was 35.

Primer paint 5—C

By mixing uniformly 200 parts by weight of the white pigment liquid A, 10 parts by weight of the black pigment liquid A, and 1 part by weight of the defoamer with respect to 200 parts by weight of the water dispersible resin D Produced a gray primer 5—C. The undercoat paint 5—C had a specular gloss of 75.

(Manufacture of colorful paints)

Paint composition 5—A

First, 200 parts by weight of the water-dispersible resin A was charged into a container, and 4 parts by weight of a water-soluble resin A and 35 parts by weight of a pigment B were stirred while stirring at a rotation speed of the stirring blade of 180 rpm. Parts, 1 part by weight of an antifoaming agent and 380 parts by weight of water were uniformly mixed to produce a transparent paint 5-A. This transparent paint 5-A had a pH of 8.1 and a specular gloss of 5.

Next, 85 parts by weight of the water-dispersible resin C was charged into another container, and 250 parts by weight of the water-soluble resin B and white were mixed while stirring at a rotation speed of the stirring blade of 180 rpm. 50 parts by weight of pigment liquid A, 50 parts by weight of black pigment liquid A, 5 parts by weight of defoamer, 50 parts by weight of water, and 3 parts by weight of reactive compound C are white by uniformly mixing Water-based paint 5—A was manufactured. The pH of the aqueous coating 5-A was ^8.9. 10 parts by weight of a 5% by weight aqueous solution of ammonium borate as a dispersion stabilizer was added to 620 parts by weight of the above transparent paint 5-A, and the mixture was uniformly mixed at a rotating speed of the stirring blade of 900 rpm, and then stirring was continued. By slowly adding and dispersing the water-based paint 5-A493 weight parts while dispersing, a paint composition 5-A in which 0.7 to 1.2 mm flat gray particles were dispersed was obtained.

Paint composition 5—B

A coating material was prepared in the same manner as for coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which 0.8 to 1.6 mm flat black particles were dispersed was used. The composition 5—B was obtained.

Paint composition 5—C

A coating material was prepared in the same manner as in coating composition 5-A except that the raw materials were used in the mixing ratios shown in Table 5, and a coating in which flat gray particles of 1.0 to 1.6 mm were dispersed. The composition 5—C was obtained.

Paint composition 5—D

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and the coating material in which 0.8 to 1.4 mm flat black particles were dispersed was used. The composition 5—D was obtained.

Paint composition 5—E

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which flat gray particles of 1.0 to 1.6 mm were dispersed. The composition 5—E was obtained.

Paint composition 5—F

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which 0.8 to 1.5 mm flat black particles were dispersed was prepared. The composition 5—F was obtained.

In the production of the coating compositions 5-E and F, a mixture of the water-based paint and the reactive compound C was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed. Paint composition 5—G

A coating material was prepared in the same manner as for coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and the coating material in which 0.8 to 1.4 mm flat gray particles were dispersed was used. The composition 5—G was obtained.

Paint composition 5—H

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. The composition 5—H was obtained.

In the production of the coating compositions 5-G and H, a mixture of the water-based paint and the reactive compound A was added to and dispersed in the transparent paint, and then the reactive compound C was further mixed.

Paint composition 5—I

A coating was prepared in the same manner as for coating composition 5-A, except that each raw material was used in the mixing ratio shown in Table 5, and a coating in which flat gray particles of 1.0 to 1.6 mm were dispersed. The composition 5—I was obtained.

Paint composition 5— J

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which 0.8 to 1.5 mm flat black particles were dispersed was used. The composition 5—J was obtained.

Paint composition 5—K

A coating material was prepared in the same manner as in coating composition 5-A except that the raw materials were used in the mixing ratio shown in Table 5, and the coating material in which 0.8 to 1.4 mm flat gray particles were dispersed was used. The composition 5—K was obtained.

Paint composition 5—L

A coating material was prepared in the same manner as in coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5, and a coating material in which flat black particles of 1.0 to 1.6 mm were dispersed. The composition 5—L was obtained.

Coating composition 5—M.

Same as coating composition 5-A except that each raw material was used in the mixing ratio shown in Table 5. A coating composition was prepared by the method described above to obtain a coating composition 5-M in which flat gray particles of 1.0 to 1.8 mm were dispersed.

Paint composition 5—N

A coating material was prepared in the same manner as in coating composition 5-A except that the raw materials were used in the mixing ratio shown in Table 5, and a coating in which flat black particles of 1.2 to 1.8 mm were dispersed. The composition 5—N was obtained.

CJl

All figures in the table are parts by weight except for pH and specular gloss

(Example 5-1)

Undercoat paint 5-A was applied to the slate plate using a wool roller at a coating amount of 0.3 kg / m ² .

After drying at room temperature for 2 hours, the amount of multi-pattern paint obtained by mixing paint composition 5-A and paint composition 5-B at a weight ratio of 50:50 was applied using a sand roller. 0. were coated with 6 kg / m ^2. Here, the state of the colored particles of the multicolored paint was observed, but no particular abnormality was observed.

Then, after drying at room temperature for 24 hours, the state of the coating film was observed. Example 5 The coating film formed in Example 11 had a smooth pattern with a mixture of white and gray, and had a uniform and uniform finish.

(Example 5-2)

Coating was performed in the same manner as in Example 5-1 except that a coating composition in which the coating composition 5-C and the coating composition 5-D were mixed at a weight ratio of 50:50 was used as the multicolor paint. Was done.

In Example 5-2, no abnormality of the colored particles was observed. Further, the formed coating film had a smooth pattern in which white, gray and black were mixed, and had a uniform and uniform finish.

(Example 5-3)

Coating was performed in the same manner as in Example 5-1 except that a coating composition in which coating composition 5-E and coating composition 5-F were mixed at a weight ratio of 5,0: 50 was used as the multi-colored paint. Was done.

In Example 5-3, no abnormality of the colored particles was observed. Further, the formed coating film had a smooth pattern in which white, gray and black were mixed, and had a uniform and uniform finish.

(Example 5-4)

Coating was performed in the same manner as in Example 5-1 except that a paint composition in which the paint composition 5-G and the coating composition 5-H were mixed at a weight ratio of 50:50 was used as the multi-color paint. Was done.

In Examples 5-4, no abnormality of the colored particles was observed. Also formed The coating film had a smooth pattern in which white, gray and black were mixed, and had a uniform and uniform finish.

(Example 5-5)

As multicolor paint, coating composition 5-I and the coating composition 5-J and 5 0: except for using mixed paint at 5 0 weight ratio, Example ₅ one: Similarly painted with L Went.

The coating film formed in Example 5-5 was a smooth pattern in which gray, black, and force S were mixed. However, the finished image was slightly inferior to Example 5— and 1 in sharpness.

(Example 5-6)

Coating was performed in the same manner as in Example 5-1 except that undercoat paint 5-B was used as the undercoat paint.

The coating film formed in Examples 5-6 had a smooth pattern in which gray and black were mixed. However, when the multi-colored paint was applied by roller, the colored particles were applied slightly unevenly, resulting in unevenness in a part of the formed coating film.

(Example 5-7)

The coating was performed in the same manner as in Example 5-1 except that a paint in which the paint composition 5—K and the paint composition 5—L were mixed at a weight ratio of 50:50 was used as the multicolor paint. went.

The coating film formed in Examples 5-7 had a smooth pattern in which gray and black were mixed. However, gray and black bleeding occurred from the colored particles.

(Reference Example 5-1)

Except that undercoat paint 5—B was used as undercoat paint, and paint composed of paint composition 51-M and paint composition 5-N was mixed at a weight ratio of 50:50 as multicolor paint. The coating was performed in the same manner as in Example 5-1.

In Reference Example 5-1, when the multicolor pattern paint was applied by roller, the colored particles were applied unevenly, resulting in significant unevenness in the formed coating film.

(Reference example 5-2)

Coating was performed in the same manner as in Example 5-1 except that undercoat paint 5-C was used as the undercoat paint. In Reference Example 5-2, when the multi-color paint was applied by the roller, the colored particles were applied unevenly, and the formed coating film was significantly uneven. Industrial applicability

The water-in-water multicolor paint composition of the present invention can form a matte coating film having excellent smoothness and sharpness. The underwater water-based multicolor paint composition of the present invention can form a uniform smooth multicolor pattern even when coating conditions such as a coating tool and a coating temperature fluctuate. Further, according to the present invention, a colorful and smooth coating film surface can be formed by coating the underwater water-based multicolored paint composition with a roller or a brush.

Claims

The scope of the claims

1. Underwater, characterized in that at least one kind of flat colored gel particles is dispersed in a matte transparent coating containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7. Water type multi-color paint composition.

2. At least one kind of flat colored gel particles is dispersed in a matte clear coating containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7,

The flat colored gel particles are characterized in that they are gelled products derived from an aqueous resin (a), a colored pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water. A water-in-water multicolored coating composition.

3. At least one kind of flat colored gel particles is dispersed in a matte transparent coating containing an aqueous resin and an extender having a refractive index of 1.4 to 1.7,

The flat colored gel particles,

It is gelled by mixing an aqueous paint containing an aqueous resin (a), a color pigment (b), and water (c) with a reactive compound (d) that can react in the presence of water. Water-based multi-color paint composition.

4. At least one kind of flat colored gel particles is dispersed in a transparent paint containing an aqueous resin.

5. At least one flat colored gel particle is dispersed in a transparent paint containing an aqueous resin,

The flat colored gel particles,

6. The component (a) is an aqueous resin (a-1) having a reactive functional group, and the component (d) is a reactive compound (d) capable of reacting with the component (a-1) in the presence of water. 6. The water-in-water multicolor paint composition according to claim 2, wherein the composition is (1).

7. The water-in-water multicolor paint composition according to any one of claims 2 to 5, wherein the component (d) is a reactive compound (d-2) capable of self-condensing in the presence of water.

The flat colored particles,

10. The water-in-water multicolor paint composition according to claim 8, wherein the component (d) is a reactive compound (d_l) capable of reacting with the component (a-1) in the presence of water. object.

11. The water-in-water multicolor paint composition according to claim 8, wherein the component (d) is a reactive compound (d-2) capable of self-condensing in the presence of water.

1 2. For building materials

After forming an undercoat layer with colored matte undercoat,

A method for forming a patterned surface, comprising forming an overcoat layer by roller coating or brush coating the water-in-water multicolored pattern coating composition according to any one of claims 1 to 11.